Dye couplers

ABSTRACT

The present invention concerns the aminophenols (I) as novel couplers ##STR1## wherein R 1  and R 2  may be the same or different and are hydrogen, alkyl and hydroxyalkyl of from 1 to about 6 carbons in the alkyl moiety, or R 1  and R 2  can also form, together with the nitrogen atom to which they are attached, a morpholine, piperidine or pyrrolidine ring, and R 3  and R 4  are hydrogen, alkyl, acyl and hydroxyalkyl having from 1 to about 6 carbons, and oxidative hair dye compositions containing same along with at least one primary dye intermediate in aqueous or hydroalcoholic media.

This is a divisional application of U.S. Ser. No. 07/353,925 filed May18, 1990, now abandoned.

FIELD OF INVENTION

This invention relates to aminophenol dye couplers useful in thecoloring of keratin fibers, especially human hair. More specifically,the present invention concerns certain oxidation dye couplers in theaminophenol class that provide blue to violet dyeouts on hair dyed withp-phenylenediamines.

BACKGROUND OF INVENTION

Three classes of components are important in oxidative hair dyeing:primary intermediates, oxidants, and couplers. The primary intermediatesare difunctional benzene derivatives capable of being oxidized withresultant development of color, e.g., ortho- and para-phenylenediaminesand para-aminophenols.

Hydrogen peroxide is the usual oxidant, although persalts of variousacids or solid organic peroxide adducts may be employed, especiallywhere a solid oxidant is desired.

The third component type--the coupler--is important in hair coloring toproduce color nuances necessary for the simulation of a natural haircolor. Couplers do not undergo facile oxidation. Rather, it is believedthat a coupler, which contains a strong electron donating group,provides a dye by reaction with electrophilic benzoquinoneimines. Thus,any aromatic compound having an amino or hydroxy group and an unblockedpara position can react with a benzoquinoneimine to produce an indo dye.However, anilines and most monohydric phenols are usually insufficientlyreactive to compete with the self-coupling reactions of the primaryintermediates under hair dyeing conditions. For this reason, the mostimportant couplers are phenols or anilines bearing a second strongelectron donor in the meta position. See generally J. F. Corbett, TheRole of Meta Difunctional Benzene Derivatives in Oxidative Hair Dyeing.I. Reaction With p-Diamines, J. Soc. Cosmet. Chem., 24, 103-134 (1973).

It is well known that the shade or color produced by a color couplerdepends on its chemical nature. For example, with p-phenylenediamine asa primary intermediate, yellow to green/brown colors are produced byresorcinol couplers, red to red-violet colors are produced bym-aminophenol couplers and blue colors are produced bym-phenylenediamine and phenolic couplers.

In the important class of blue couplers, phenolic compounds in generalform color far too slowly to be of practical commercial importance--theexception being 1-naphthol, which forms color at an acceptable rate, buthas the disadvantage of poor solubility in hair dyeing systems,particularly in recently developed, highly aqueous systems. As analternative, m-phenylenediamine couplers can be used. However, they havethe disadvantage of producing dyes that slowly change color from blue tored over a period of days or weeks.

U.S. Pat. No. 4,797,130 to Clausen, et al. discloses compounds havingthe structures ##STR2## wherein the group R¹ and R² may includehydrogen, alkyl, hydroxyalkyl, aminoalkyl, and the like. Unlike the dyecoupler compounds of the present invention, the compounds (II) areprimary intermediates, that is, color is developed by oxidizing thesecompounds, e.g., with hydrogen peroxide, to form benzoquinoneimines thatare reactive with a color-producing coupler. Placement of the hydroxyand amino groups para to each other is essential for these compounds(II) to behave as primary intermediates.

U.S. Pat. No. 3,210,252 to Blanke, et al. discloses5-amino-2-methylphenol as a coupler. When this coupler is used to couplewith p-phenylenediamine, a red-violet shade is obtained on hair.

U.S. Pat. No. 4,065,255 to Andrillon, et al. discloses a coupler of thestructure ##STR3## where R is a hydroxyalkyl of 1-4 carbon atoms. Ared-violet color is obtained on gray hair when the coupler (III) with Rdefined is hydroxyalkyl containing 1 to 4 carbons is reacted withp-phenylenediamine.

U.S. Pat. No. 4,588,410 to Konrad discloses couplers of the structure.##STR4## wherein R is hydrogen, methyl or hydroxyethyl. The compound(IV) is especially useful for providing red tones. More specifically,compound (IV) when R is hydrogen couples with p-phenylenediamine to giveintense mahogany coloration on human hair.

U.S. Pat. No. 3,834,866 to Pum discloses 5-aminoguaiacol derivatives (V)useful as coupling agents ##STR5## wherein when R is hydrogen, a darkmaroon shade is produced with p-phenylenediamine on white virgin hair.

U.S. Pat. No. 3,712,790 to Kalopissis, et al. discloses the coupler##STR6## wherein R is hydrogen, alkyl, hydroxyalkyl, acyl, orN-alkylated or unsubstituted aminoalkyl or carbamylmethyl group, thealkyl groups of these radicals having 1-6 carbons.

U.S. Pat. No. 4,094,635 to Bugaut, et al. discloses m-aminophenolsulfonamide couplers in hair dye compositions. When reacted withp-phenylenediamine, a red-violet coloration on natural white hair isobtained.

It is apparent that m-aminophenols bearing a substituent ortho and parato the hydroxy and amino groups, respectively, produce red to red-violetcolors with p-phenylenediamine. It is unexpected that when thissubstituent is an aminomethyl group, intense blue to blue-violet colorsare obtained.

SUMMARY OF THE INVENTION

It is an object of this invention to provide hair dye couplers for usein oxidative hair dye compositions.

It is a primary object of the present invention to provide aminophenoldye couplers useful in oxidative hair dye compositions that produce blueto violet shades on hair when the primary intermediate is ap-phenylenediamine.

It is another object of the present invention to provide an oxidationhair coloring process suitable to provide hair with long-lasting naturalcolor tones among which is a blue to violet color tone occasioned by thecouplers of the present invention.

These and other benefits and advantages of the present invention aredisclosed more fully in the detailed description of the invention, asummary of which follows.

In one aspect the present invention concerns novel compounds having thestructure (I) ##STR7## wherein R₁ and R₂ may be the same or differentand are hydrogen, alkyl and hydroxyalkyl of from 1 to about 6 carbons,or R₁ and R₂ form, together with the nitrogen atom to which they areattached, a morpholine, piperidine or pyrollidine ring, and R₃ and R₄are hydrogen, alkyl, acyl and hydroxyalkyl having from 1 to about 6carbons.

A further aspect of the present invention concerns a dyeing compositionuseful in permanently dyeing keratin fibers including human hair, thedyeing composiiton comprising the coupler (I) and a primaryintermediate.

In yet another aspect, the present invention concerns a process forpermanently dyeing hair comprising admixing the dyeing composition withan oxidizer, applying the mixture for a predetermined period of time,and rinsing the mixture from the hair.

DETAILED DESCRIPTION OF INVENTION

The m-aminophenol compounds (I) of the present invention are quitesuitable for use generally as dye couplers in oxidative dyecompositions. The oxidative dye composition further contains a primaryintermediate such as p-phenylenediamine, the composition beingoxidizable with hydrogen peroxide or other oxidant to produce an arrayof colors. Especially suitable couplers (I) are

5-amino-2-[(dimethylamino)methyl]phenol;

5-amino-2-{[bis(2-hydroxyethyl)amino]methyl}phenol;

5-amino-2-(morpholinomethyl)phenol;

5-amino-2-(pyrrolidinomethyl)phenol;

5-amino-2-(aminomethyl)phenol;

5-dimethylamino-2-[(dimethylamino)methyl]phenol;

5-dimethylamino-2-(pyrrolidinomethyl)phenol;

5- acetamido-2-[(dimethylamino)methyl]phenol,

and their acid, especially hydrochloride, salts.

In a particular useful and preferred aspect of the present invention, ithas been found that certain of the m-aminophenol couplers (I) and theiracid salts, when employed in an alkaline oxidizing medium with asuitable primary intermediate, especially p-phenylenediamine primaryintermediates, unexpectedly impart to the keratin fibers a blue toviolet shade. Moreover, it has also been found that surprisinglylong-lasting keratin fiber shades are obtainable, which shades resistfading caused by weathering and/or light. In this regard, they are morelong-lasting than the blue to violet shades obtained whenm-phenylenediamines are employed as the coupler. The blue to violetshades produced by the couplers (I) when employed withp-phenylenediamines are particularly important to achieve a true blackhair color having a realistic tonal impression.

It should be understood that the blue to violet colors referred toherein are the actual hues obtained when the hair is dyed with thecoupler (I) as the only coupler and the suitable primary intermediate,i.e., a primary intermediate used in connection with this preferredaspect of the invention, such as p-phenylenediamine, that provides witha coupler (I) the blue to violet color to the hair fibers. The suitableprimary intermediate may be easily determined by actual testing with thedislosed couplers of the present invention, in accordance with theprocedures outlined in the examples. As one skilled in the art realizes,the color obtained by the mere admixture of the couplers (I) and thesuitable primary intermediates under oxidative conditions is notnecessarily the same hue obtained when used to actually dye hair. Ofcourse, the couplers (I) and the suitable primary intermediates areseldom used independently of other dye constituents. Rather, asdescribed elsewhere in this application, a plurality of couplers areused with one, two or more primary intermediates to obtain the desiredcolor imparted to the hair, which color will be a blend of theaforementioned blue to violet shade as well as other shades provided bywhatever additional constituents are present.

Particularly preferred couplers in this preferred aspect of theinvention are

    5-amino-2-[(dimethylamino)methyl]phenol;

    5-amino-2-(pyrrolidinomethyl)phenol;

    5-amino-2-(aminomethyl)phenol,

and their acid, especially hydrochloride, salts.

The dye compositions of the present invention comprise from about 0.001to about 10%, preferably from about 0.05 to about 5%, most preferablyfrom about 0.1 to about 2.5%, of a coupler, all or part of which couplermay be the coupler (I), from about 0.001 to about 10%, preferably fromabout 0.05 to about 5%, most preferably from about 0.2 to about 2.5%, ofa primary intermediate, and water. The proportions and amounts of theseveral constituents in the hair dye composition will depend on thenature and amount of the dye components, the tonal impression to becreated, and the color of the hair to be dyed. Whether to use two ormore of the couplers or whether to include two or more primaryintermediates will depend on the shade of the color desired. Generally,the coupler to primary intermediate molar ratio is from about 0.1:1 toabout 10:1, preferably from about 1:1 to about 4:1.

The dye compositions of the present invention may comprise the coupler(I) and one or more additional coupler compounds, for example,m-phenylenediamines such as 2,4-diaminoanisole and2,4-diaminophenoxyethanol; other m-aminophenols such as m-aminophenol,5-amino-2-methylphenol, 5-(N-2-hydroxyethylamino)-2-methylphenol,2-methyl-5-carbamylmethylaminophenol and 5-amino-2,6-dimethylphenol;m-acetamidophenols such as 5-acetamido-2-methylphenol; m-ureidophenols;resorcinols, and heterocyclic couplers such as 6-hydroxybenzomorpholine,2,6-diaminopyrridine and 1-phenyl-3-methylpyrazolone.

The primary intermediates incorporated in the dye composition of thepresent invention are preferably p-phenylenediamines, for example, dyecompounds of the formula ##STR8## wherein R₁ and R₂ are substituentgroups including hydrogen, alkyl, hydroxyalkyl, aminoalkyl, andacylaminoalkyl, R₃ is hydrogen, alkyl, alkoxy or halogen, and R₄ ishydrogen, halogen, alkyl or alkoxy, the alkyls having from 1 to 6,preferably from 1 to 4 carbons, the compounds (VI) being as a free baseor in the form of an acid additive salt such as a hydrochloride, andp-aminophenols, for example, dye compounds of the formula ##STR9##wherein R and R' are hydrogen, alkyl, hydroxyalkyl, alkoxy, or halogen,the alkyls having 1 to 6 carbons.

Illustrative compounds (VI) are p-phenylenediamine,2,6-dimethyl-3-methoxy-p-phenylenediamine dihydrochloride;3-methoxy-4-amino-N,N-dimethylaniline sulfate;N,N-bis(2-hydroxyethyl)-p-phenylenediamine sulfate. Illustrativecompounds (VI') are p-aminophenol; 4-amino-2,6-dimethylphenol;4-[(2-acetamidoethyl)-amino]phenol sulfate; 3-methyl-4-aminophenolhydrochloride, and 2,5-dimethyl-4-aminophenol. p-Phenylenediamine,p-toluenediamine, p-aminophenol andN,N-bis(2-hydroxyethyl)-p-phenylenediamine sulfate are preferred.

Two or more primary intermediate compounds (VI) and (VI') may beincorporated into the dye compositions of the present invention. Thehair dye composition disclosed herein may also include, in addition tothe primary intermediate compounds (VI), one or more dyes such asanthraquinones, nitrobenzenes, diphenylamines, azo dyes, indoanilines,indophenols and indamines.

The dye compositions of the present invention include an aqueous,alcoholic or hydroalcoholic medium as a vehicle or carrier. The alcoholmoiety, if present, is usually a lower alkanol, of from 1 to 6 carbons,especially ethanol or propanol, but may be a glycol having a total of upto about 10 carbons, especially less than 6 carbons, such as propyleneglycol, butyl glycol and diethyleneglycol monobutyl ether. The vehicleis generally from about 1 to 75% by weight of the composition.Typically, the alcohol moiety, if present, comprises 10 to about 50% byweight of said vehicle, and the vehicle is typically from about 10 toabout 50% by weight of the composition.

The compositions of the present invention may further include acationic, anionic or amphoteric surface-active agent in an amount of upto about 20% by weight, preferably from about 0.5 to about 10%.Representative surface-active agents include octoxynol-1, nonoxynol-4,oleic acid and salts thereof and lauric acid and salts thereof.

The hair dye compositions of the present invention may also include oneor more adjuvants such as perfumes, antioxidants such as sodium sulfiteand sodium thioglycolate, sequestering agents such as EDTA, alkalizingagents such as ammonia or an alkanolamine, acidifying agents such asoleic, acetic acid and phosphoric acids. These adjuvants are present inan amount effective to provide their functional activity. The pH of thecompositions of the present invention range typically from about 8 toabout 11.

Although preferred to admix the developer, e.g., hydrogen peroxide, andthe dyeing composition at the moment of use, compositions containinghydrogen peroxide are within the scope of this invention. The hydrogenperoxide developer is typically an aqueous solution of H₂ O₂ having aconcentration between 5 and 50 volumes, preferably between 10 and 40.

Upon mixing with the developer, the primary intermediate is oxidized andthereafter reacts with the coupler to provide the intended color. Aftermixing, the mixture is applied to hair for typically from about 5 toabout 60 minutes, especially between about 20 and about 45 minutes. Asknown in the art, the dyeing composition often contains more than oneprimary intermediate and more than one coupler, to provide the shade ofhair color desired.

The invention is further described by way of the examples below.

EXAMPLE 1 Synthesis of 5-amino-2-(aminomethyl)phenol dihydrochloride (1)Synthesis of 5-acetamido-2-[(2-chloroacetamido)methyl]phenol

A solution of 3-acetamidophenol (1.5 g, 10 mmol) andN-(hydroxymethyl)-2-chloroacetamide (1.2 g, 10 mmol) was stirred in 50ml of 20% HCl in methanol at room temperature for 2 days. After removalof solvent, the desired product was isolated in 20% yield (0.51 g, 2mmol) by chromatography (silica gel, eluted with ethyl acetate andhexane, 40/60).

(2) Hydrolysis of 5-acetamido-2-[(2-chloroacetamido)methyl]phenol

5-Acetamido-2-[(2-chloroacetamido)methyl]phenol (0.51 g, 2 mmol) washydrolyzed in 10 ml of 20% HCl in methanol at 80° for 1 hour.5-Amino-2-(aminomethyl)phenol was isolated in 90% yield (0.36 g, 1.8mmol) as its dihydrochloride salt. Its NMR (D₂ O) was δ7.2(d, J=7.5 Hz,1H), 6.7(d, J=7.5 Hz, 1H), 6.6(6s, H), 3.9(6s, 2H).

EXAMPLE 2 Synthesis of 5-dimethylamino-2-[(dialkylamino)methyl]phenol

An equimolar solution of 3-dimethylaminophenol, formaldehyde and asecondary amine recited below in Table I was stirred in methanol at roomtemperature until there was no further reaction. The Mannich base wasisolated by filtration and purified by recrystallization.

                  TABLE I                                                         ______________________________________                                        Secondary                      Yield                                          Amine      Product             %                                              ______________________________________                                        Morpholine 5-dimethylamino-2-  80                                                        (morpholinomethyl)phenol*                                          Dimethylamine                                                                            5-dimethylamino-2-  70                                                        [(dimethylamino)methyl]phenol**                                    ______________________________________                                         *NMR (acetoned.sub.6)δ6.8(d, J =6Hz, 1H), 6.1(m, 2H), 3.6(m, 4H),       3.5(s, 2H), 2.8(s, 6H), 2.5(m, 4H)                                            **NMR (acetoned.sub.6)δ6.8(d, J=10Hz, 1H), 6.2(m, 2H), 3.7(s, 2H),      2.9(s, 6H), 2.3(s, 6H)                                                   

EXAMPLE 3 Synthesis of 5-amino-2-[(dialkylamino)methyl]phenoldihydrochloride (1) Synthesis of5-acetamido-2-[(dialkylamino)methyl]phenol

An equimolar solution of 3-acetamidophenol, formaldehyde and a secondaryamine recited in Table II below was stirred in methanol at roomtemperature until there was no further reaction. The Mannich base wasisolated by filtration and purified by recrystalization.

(2) Hydrolysis of 5-acetamido-2-[(dialkylamino)methyl]phenol

5-Acetamido-2-[(dialkylamino)methyl]phenol was hydrolyzed in 20% HCl inmethanol at 80° for 1 hour. 5-Amino-2-[(dialkylamino)methyl]phenol wasisolated as its dihydrochloride salt.

                  TABLE II                                                        ______________________________________                                        Amine     Product                Yield                                        ______________________________________                                        Pyrrolidine                                                                             5-acetamido-2-         44                                                     (pyrrolidinomethyl)phenol*                                          Diethanolamine                                                                          5-acetamido-2-{[bis    73                                                     (2-hydroxyethyl)amino]methyl}phenol**                               ______________________________________                                         *NMR (acetoned.sub.6)δ9.8(6s, 1H), 7.2(6s, 1H), 7.0-6.8(m, 2H),         3.7(6s, 2H), 2.6(6s, 4H), 2.1(6s, 3H), 1.8(6s, 4H)                            **NMR (acetoned.sub.6)δ10.3(6s, 1H), 9.0(6s, 1H), 7.5(d, J=3Hz, 1H)     7.3(d, J=8Hz, 1H), 7.0(dd, J=8Hz, J=3Hz, 1H), 4.3(d, J=3Hz, 2H), 3.8(m,       4H), 3.2 (m, 4H), 2.0(s, 3H)                                             

EXAMPLE 4 Synthesis of 5-amino-2-[(dimethylamino)methyl)]phenoldihydrochloride

Acetic anhhydride (21.2 ml, 220 mmol) was slowly added to a suspensionof m-aminophenol (24.0 g, 220 mmol) in 60% of crushed ice and 60 ml ofcold water. The reaction mixture was vigorously stirred for 30 minutes.The white precipitate was filtered, washed with cold water, andair-dried to give 30.5 g (92%) of pure 3-acetamidophenol, m.p. 147°-149°C.

To a solution of 3-acetamidophenol (15.25 g, 101 mmol) in 40%dimethylamine (13.8 ml, 122 mmol) and 13 ml of methanol, was added 37%formalin (8.3 ml, 101 mmol). The reaction mixture was placed in an icebath just after the precipitate formed (about 15-30 minutes). The whiteprecipitate was filtered after 10-30 minutes, washed with cold water,and air-dried to give 13.7 g (65%) of5-acetamido-2-[(dimethylamino)methyl]phenol, m.p. 133°-135° C.

5-acetamido-2-[(dimethylamino)methyl)]phenol (5.0 g, 24 mmol) wasdissolved in 30 ml of HCl/methanol (about 22%) and refluxed at 80° C.(oil bath) for 1.5 hours. The white compound, which precipitated out ofsolution, was filtered to give 4.4 g (77%) of5-amino-2-[(dimethylamino)methyl]phenol dihydrochloride (m.p. 185°-190°C.). Its NMR (D₂ O) was δ6.7 (d, J=8 Hz), 6.2 (d, J=2 Hz), 6.0 (dd, J=8Hz, J=2 Hz, 1H), 2.0 (s, 3H).

The examples that follow demonstrate the use of the m-aminophenol dyecouplers of the present invention. Examples 11-15 illustrate thepreferred embodiment of the present invention, wherein certain compounds(I) provide, with p-phenylenediamine, a distinctively blue color whenapplied to hair.

EXAMPLE 5

5-Dimethylamino-2-[(dimethylamino)methyl]phenol (0.7%) was mixed withp-phenylenediamine (0.3%) in aqueous ethanol (water:ethanol=2:1 v/v).After mixing with equal volume of hydrogen peroxide (30 volume), andadjusting the pH to 10 with ammonium hydroxide, the mixture was appliedto gray hair for 30 minutes. A red-violet shade was obtained aftershampoo and rinse.

EXAMPLE 6

A water/ethanol (2:1 v/v) solution containing 0.7% p-phenylenediamineand 1% 5-amino-2-(morpholinomethyl)phenol was mixed with equal volume ofhydrogen peroxide (30 volume). Ammonium hydroxide was used to raise thepH to 10. The final solution was employed to treat blended gray hair for30 minutes. This imparted a red-violet color on the tress after shampooand rinse.

EXAMPLE 7

An aqueous solution of p-phenylenediamine (0.16%) and5-amino-2-{[bis(2-hydroxyethyl)amino]methyl}phenol dihydrochloride(0.6%) was prepared. An equal part of 20-volume hydrogen peroxide wasadded, and the pH was adjusted to 9.7 with monoethanolamine (MEA). Thismixture applied for 30 minutes to gray hair imparted, after rinsing andshampooing, a purple color.

EXAMPLE 8

The same as Example 7 but with5-acetamido-2-[(dimethylamino)methyl]phenol as the coupler. A lightbrown color was obtained on gray hair after 30 minutes of treatment.

EXAMPLE 9

The same as Example 7 but with5-dimethylamino-2-(morpholinomethyl)phenol as the coupler. A light browncolor was imparted on gray hair.

EXAMPLE 10

p-Aminophenol (0.22%) and 5-amino-2-[(dimethylamino)methyl]phenoldihydrochloride (0.48%) were dissolved in an aqueous medium. Aftermixing with an equal part of 20-volume hydrogen peroxide, the pH wasraised to 10 with MEA. This final solution was used to dye gray hair.After 30 minutes the hair was rinsed and shampooed. The hair had anatural brown tone.

EXAMPLE 11

p-Phenylenediamine (0.16% by wt.) and5-amino-2-[(dimethylamino)methyl]phenol dihydrochloride (0.48% by wt.)were dissolved in an aqueous solution. An equal part of 20-volumehydrogen peroxide was added, and the pH of this mixture was adjusted toabout 9 with concentrated ammonium hydroxide. This final solution wasapplied to treat gray hair for 30 minutes to give a blue-violet colorafter shampooing. When the abovementioned phenol was replaced with5-amino-2-methylphenol, a red-violet shade was obtained, as indicated inTable III below.

                  TABLE III                                                       ______________________________________                                                       Hunter Tristmulus Values                                       Coupler          L          a     b                                           ______________________________________                                        5-amino-2-[(dimethyl-                                                                          13.8       6.0   -8.0                                        amino)methyl]phenol.2HCl                                                      5-amino-2-methylphenol                                                                         11.7       9.4   -0.1                                        ______________________________________                                    

In the Hunter system, the L value indicates intensity of the colorobtained. The lower the value, the darker the color. The a valueindicates the degree of redness or greenness of the color obtained. Thehigher the a value, the redder the color. The lower the a value, thegreener the color. Similarly, the b value indicates the degree ofyellowness or blueness of the color. The higher the b value, the moreyellow the color obtained, while a low b value signifies a more bluecolor. As seen from Table III, the color obtained for5-amino-2-[(dimethylamino)methyl]phenol dihydrochloride is significantlyless red and more blue than that obtained with the conventional5-amino-2-methylphenol coupler.

EXAMPLE 12

The following composition was mixed with an equal volume of 20-volumehydrogen peroxide and left on bleached hair for 30 minutes:

    ______________________________________                                                               Wt. (gm.)                                              ______________________________________                                        p-phenylenediamine       0.27                                                 5-amino-2-[(dimethylamino)methyl]phenol.2HCl                                                           0.6                                                  Sodium lauryl sulfate    3                                                    Oleic acid               20                                                   Propylene glycol         8                                                    Octoxynol-1              9                                                    Isopropyl alcohol        8                                                    Ammonium hydroxide       8                                                    Erythorbic acid          0.3                                                  Water                    Q.S. 100                                             ______________________________________                                    

After rinsing and shampooing, a blue-violet color was obtained on thehair.

EXAMPLE 13

p-Phenylenediamine (0.27%) and 5-amino-2-(pyrrolidinomethyl)phenoldihydrochloride (0.9%) were dissolved in an ethanolic solution(water:ethanol=7:3 v/v). An equal part of 20-volume hydrogen peroxidewas added, and the pH of this mixture was brought up to about 9.6 withconcentrated ammonium hydroxide. This solution was applied to regulargray hair for 30 minutes and a blue-violet shade was obtained.

EXAMPLE 14

p-Phenylenediamine dihydrochloride (0.3%) and5-amino-2-(aminomethyl)phenol (0.35%) were mixed in an ethanolicsolution (water:ethanol=75:25 v/v). Three parts of this solution and twoparts of a 20-volume hydrogen peroxide were then combined, and the pHwas adjusted to 9.7 with concentrated ammonium hydroxide. A violet colordeveloped on gray hair after 30 minutes, while p-phenylenediamine with5-amino-2-methylphenol gave a color having a more reddish hue.Tristimulus measurements of these two tresses again show that the tressdyed with the coupler of the present invention has a lower a value,i.e., less red hue (more blue hue), than the tress dyed with theconventional m-aminophenol coupler.

EXAMPLE 15

N,N-bis(2-hydroxyethyl)-p-phenylenediamine sulfate (0.45%) was used toreplace p-phenylenediamine in Example 11. The mixture applied for 30minutes to gray hair imparted, after rinsing and shampooing, a bluecoloration.

We claim:
 1. A hair dye composition comprising by weight of thecomposition from about 0.001 to about 10% of an oxidative dye coupler ofthe structure: ##STR10## wherein R₁ and R₂ may be the same or differentand are hydrogen, C₁ -C₆ alkyl or C₁ -C₆ hydroxyalkyl, or form with thenitrogen atom to which they are attached a morpholine, piperdine orpyrollidine ring, and R₃ and R₄ are hydrogen, C₁ -C₆ alkyl, C₁ -C₆hydroxyalkyl or C₁ -C₆ acyl, and from about 0.001 to about 10% of aprimary intermediate.
 2. The composition of claim 1 wherein R₁ and R₂are methyl.
 3. The composition of claim 1 wherein R₁ and R₂ arehydroxyethyl.
 4. The composition of claim 1 wherein R₁ is methyl and R₂hydroxyethyl.
 5. The composition of claim 1 wherein R₁ and R₂, togetherwith the nitrogen to which they are attached, form a morpholine ring, apiperidine ring, or a pyrollidine ring.
 6. The composition of claim 1wherein the coupler is selected from the group consistingof5-amino-2-(aminomethyl)phenol; 5-dimethyl-2-(morpholinomethyl)phenol;5-dimethylamino-2-[(dimethylamino)methyl]phenol;5-acetamido-2-[(dimethylamino)methyl]phenol;5-acetamido-2-{[bis(2-hydroxyethyl)amino]methyl}phenol;5-acetamido-2-(pyrrolidinomethyl)phenol, and their acid salts.7. Thecomposition of claim 2, 3, 4 or 5 wherein R₃ and R₄ are hydrogen, methylor ethyl.
 8. The composition of claim 1 wherein the primary intermediateis selected from the group of p-phenylenediamines and p-aminophenols. 9.An aqueous hair dye composition comprising on a weight basis from about0.001 to about 10% of at least one oxidative dye coupler of thestructure ##STR11## wherein R₁ and R₂ may be the same or different andare hydrogen, alkyl and hydroxyalkyl of from 1 to about 6 carbons, orform with the nitrogen atom to which they are attached a morpholine, apiperidine or a pyrollidine ring, and R₃ and R₄ are hydrogen, alkyl,hydroxyalkyl and acyl of from 1 to 6 carbons, and from about 0.001 toabout 10% of a primary dye intermediate, the compound (I) together withthe primary dye intermediate, in aqueous media and following developingwith an oxidizer, providing hair treated therewith with a blue to violethue.
 10. The composition of claim 9 wherein the primary intermediatesare selected from the group consisting of p-phenylenediamines and theiracid salts.
 11. The composition of claim 9 wherein the primaryintermediates are selected from the group consisting of p-aminophenolsand their acid salts.
 12. The composition of claim 10 wherein thep-phenylenediamines have the structure ##STR12## wherein R₁ and R₂ arehydrogen, alkyl, hydroxyalkyl, aminoalkyl, acylaminoalkyl, R₃ ishydrogen, alkyl, alkoxy or halogen, and R₄ is hydrogen, halogen, alkyl,and alkoxy, the alkyl and acyl groups having from 1 to about 6 carbons.13. The composition of claim 11 wherein the p-aminophenols have thestructure ##STR13## wherein R and R' are hydrogen, alkyl, hydroxyalkyl,alkoxy, or halogen, the alkyls having 1 to 6 carbons.
 14. Thecomposition of claim 12 wherein the dye coupler (I) is selected from thegroup consisting of5-amino-2-[(dimethylamino)methyl]phenol;5-amino-2-(aminomethyl)phenol; and 5-amino-2-(pyrrolidinomethyl)phenol,and the corresponding acid salts thereof.
 15. The composition of claim12, 13 or 14 wherein the coupler (I) is present in an amount of fromabout 0.05 to about 5%, and wherein the primary intermediate is presentin an amount of from about 0.05 to about 5% by weight.
 16. Thecomposition of claim 12, 13 or 14 further comprising one or moreoxidative dye couplers that are not the compound (I), the couplerconcentration in total being less than about 10% by weight of thecomposition.
 17. The composition of claim 16 wherein said compositionwhen developed with an oxidizer provides on hair a black hue.
 18. Thecomposition of claim 9 wherein the coupler (I) is5-amino-2-[(dimethylamino)methyl]phenol and its salts and the primaryintermediate is selected from p-phenylenediamine,N,N-bis(2-hydroxyethyl)-p-phenylenedimaine and their acid salts.
 19. Thecomposition of claim 9 wherein the coupler (I) is5-amino-2-(aminomethyl)phenol and its acid salts and the primaryintermediate is p-phenylenediamine and its acid salts.
 20. Thecomposition of claim 9 wherein the coupler (I) is5-amino-2-(pyrrolidinomethyl)phenol and its acid salts and the primaryintermediate is p-phenylenediamine and its acid salts.
 21. Thecomposition of claim 9 further comprising an alcoholic cosolvent in theamount of from about 1 to about 25% by weight of the composition. 22.The composition of claim 10 or 11 further comprising one or more of thefollowing in a functionally effective amount: surfactant, antioxidant,sequestrant or chelant, alkalizing agent, or acidifying agent.
 23. Thecomposition of claim 9 wherein the hair color obtained with the compound(I) and the primary intermediate is a blue hue.
 4. A method of dyeinghair comprising the steps of developing the dye composition of claim 1,9, 12, 14, 17, 18, 19 or 20 with an oxidizer, applying the developedhair dye composition to hair for sufficient time to color the hair, andrinsing the residual hair dye composition from the hair.